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Electrophilic gold(I) complexes of diphenyl- and dicyclohexylphosphino-based KITPHOS monophosphines catalyze the 5-exo-dig cycloisomerization of a range of propargyl amides to afford the corresponding alkylidene oxazolines; in all cases catalysts formed from diphenylphosphino-substituted KITPHOS monophosphines outperformed their dicyclohexylphosphino counterparts as well as that based on triphenylphosphine, an indication that the biaryl/biaryl-like framework may be responsible for imparting high catalyst efficiency.